Process for reduction of phosphate rock



Lam-,236

May 31, 1932. J. D. MORGAN PROCESS FOR REDUCTION OF PHOSPHATE ROCK Ja@ #290@ 37:31u/ wwo @Ewan 9.8

Ma.)r 31', 1932. D, MORGAN .11,861,236

PROCESS FOR REDUC'ToN oF PH'osPHATE ROCK Filed 'May 11. 192s 3 sheets-snm 2 May 3l, 1932.

J. D. MORGAN PROCESS FOR REDUCTION OF PHOSPHATE ROCK Filed May 11,v 192s 5 Sheets-Sheet 3 vwewoz JOHN D. MORGAN Patented May 31, 1932 uNrrlezDk STATES PATENT OFFICE JOHN D.MCRGAN, or' MAPLEWooD, NEW JERSEY, AssIGNoR 'ro DCHERTY RESEARCH COMPANY, or' NEW YORK, N. Y., A CORPORATION or DELAWARE PROCESS FOR REDUCTION F PHOSPHATE ROCK The present invention `relates to the production of phosphorus or phosphate materials from native or other phosphates.

A It'has been proposed to reduce phosphates, ii'such las native calcium phosphate or phosphate rock, by means of carbon in an electric or other furnace. Diiiiculty has been encountered, however, in obtaining good yields of VMphosphoric material in proportion to the lphosphorus in the phosphate treated. It has been attempted to overcome this difficulty by introducing silica into the charge in addition to the carbon and by fusing the charge to Wproduce a fluid sla Another proposal for l'increasingthe yielcgl of phosphoric material has been to use approximately'twice as much carbon as theoretically required for the reduction of the phosphorus in addition to Mrsilica, fusion being avoided in this case. 29* It is one of the principal objects of the present invention to provide a process of reducing phosphates which shall give good yields of phosphoric material at a reasonable rice. Y Y

2F54'Lp In the reduction of phosphates by carbon, phosphorus and carbon monoxide are formed as the primary products. These substances have a high heat value. If this heat value is Trecovered, vobviously the cost of the phosphoric material is reduced, Dificulty has been encountered, however, in utilizing the heat of the primary products of the process.

Another object of the invention is to ro- 4l-`-vide a simple and efficient method of utiliz- 3'5'"ing the heat value of the primary productsof the reduction ofphosphates.

It has been found in practice that the electric furnace is the most convenient for the ,vreduction of phosphates. However, if elec tri`city is employed for heating the charge, the vcost is-high at the ordinary rates vwhen using twenty-four hour electricpower. If the process and apparatus therefore can be iso arranged that the operationmay be shut J down during a part of eachr day as desired in order'that theprocess load shall avoid the periodof peakV load on the electrical system andso'obtain more'fa'vorable rates for elec- ;tric power, the cost per pound of the phos- 'phoric material produced by the process can y Application led May 11,

192s. serial No. V276,340.

be materially reduced. This involves, however, that the fixed charges per KW of the furnace shallbe less than the fixed charges per KW of the power plant and line between the power plant and the furnace.

It is another of the objects of the present.

invention to provide an electric furnace so arranged and suiiciently low in first cost that it is technically and commercially feasible to shut it down during a portion of the da Further objects and advantages o lthe present invention will be evident to those skilled in the arts from the following description taken in connection with the accompanying drawings in which:

Fig. l is a diagrammatic view of an apparatus according to the present invention and adapted to carry out the process according to the present invention;

Figs. 2 and 3 are elevations, partl in section, and parts being broken away o the up per and lower ends of an electric furnace according to the present invention;

Fig. et is an elevation of the furnace taken from the right of Fig. 2;

Fig. 5 is an end view of the furnace taken from the left of Fig. 3;

Fig. 6 is a section of the furnace taken on the line 6-'-6 of Fig. 2 looking in the direction of the arrows;

Fig. 7 is a section of the furnace taken on the line 7-7 of Fig. 3 looking in the direction of the arrows;

Fig. 8 is a section of the furnace taken on the line 8 8 of Fig. 3 looking in the direction ofthe arrows;

Fig. 9 is a section taken on the line 9-9 of Fig. 8 looking in the direction of the arrows;

Fig. l0 is a plan vview of one section of a Cottrell precipitator such as may be used in connection with the present invention and which is indicated diagrammatically in Fig. l.

Fig. 11 is a vertical sectional view of the 9 upper end of the precipitator section illustrated in Fig. 10 as it appears when equipped with one type of insulator according to the present invention;

Fig. l2 is a view similar to Fig. 11 i11us trating the upper end of the precipitator section as equipped With another form of insulator according to the present invention.

In the process according to the present invention, a phosphate preferably native rock phosphate (tricalcium phosphate), is

prepared f or reduction With carbon by being are mixed preferably in the proportions of 75 parts of vphosphate rock to 25 parts of carbon and 10' parts of calcined dolomite by Weight. rlhe proportion of carbon just stated is approximately that theoretically required for the complete reduction of phosphorus in tricalcium phosphate, it being possible according to the present invention to obtain substantially complete reduction of the phosphorus and a high yield of phosphatic material when using only the theoretical amount of carbon. It has been found that potash bearing minerals are reduced and the potash liberated under the conditions used to reduce the phosphates. Felspar or other potash bearing minerals may be added tothe charge and, in this case, the potash appears in the recovered products in combination with phosphoric acid. lZVhen` a potash-bearing mineral is added to the charge, it is preferredalso to increase the amount of carbon above that requir-ed to reduce the phosphate. The amount of' dolomite mentioned is merely that sufficient to hold the parts of the charge together. The charge is formed pref erably in the proportions j'ust stated and is thoroughly mixed, after which Water is added to make the mass somewhat plastic. The mixture is then extruded or pressed into briquets or plates,r which preferably are of rectangular form.. It is preferable that the thickness of the plates. be not greater than one half inch. lf a ribbed or groovedl section is used, it is preferred that no point Within the interior of a given plate or briquet be at a *greaterfdistance than one fourth inch from some'point on the surface of the briquet.,

This is for the reason that experiment has shown that the rate at which the phosphorusl is'driven olf from a briquet at a given temperat-ure decreases very rapidly as the thickness is increased above one half inch. In fact,v in a given experiment, When operating with plates one-fourth inch thick, 80% of the phosphorus in the plates Was volatilizedf in fifteen minutes, Whereas, with plates one halfinch thick over 70% was volatilized after heating for one half hour. When the thickness of the plates was increasedto one inch,

over one hour Was required to, obtain 70% volatilization.VA Therefore, the platesshould be as thin as possible consistent with the strength necessary to permit them being conveniently introduced into and handled in the furnace.

The briquets or plates, after being formed, are passed through a furnace having' an inclined hearth and are preferably preheated in the entering end of the furnace by combustion of phosphorus and gases developed in the reaction zoneI of the furnace` The charge, after leaving the pneheater zone, passes down into the reaction zone Where it is heatedl to a somewhat higher temperature by radiation from electrically heated resistance elements. In the reaction zone, phosphorusv is evolvedA from. theY chal: e. ami at the same time,consilderable quantities of car bon monoxidey and small. antites of hy drogen are formed. Preferblac cordingfto the present invention,y the charge. is heated to approximately 2400:o F. by combustion of the phosphorus and carbon monoxide While the charge is in the preheater zone, and the temperature is raised preferably to, about. 25500 F. in the reactionzone ofthefurnace. lt is important that the charge sha1-l, not fusel While passing through; the furnace and its composition isl determined in partby this. consideration. If the chargefuses it becomes more difficult, to Vprevent the. charge from sticking to the hearth and itY rdilflilcult, also. to regulate the movement ofthecharge alongthe` hearth.

The phosphorus and carbon monoxideare burned in the preheating zone by atmospheric oxygen admitted for this pur ose, thereby converting thephosphorus into Q1 (phosphoric anhydride)V and the CQto. 0Q2.. If desired, ammonia may be admitted to the preheater zone toI increase the amount of heat developed in this zone andV to convert some of the phosphoric acid intoaminoninm phosphate, there always bein some water present sof that some of the. p'osphoric an.- liydride is converted into phosphoric acid.4 If' desired, further, also,. ammoni'afwater may be admitted to the preheating: zone toi fur` ther convert the P205 into. ammonium phosphate. Moreover, when fellspan or: other source ofpotash, is addeclto the charge, more or less ofthe P2()5 is converted to, acidpotassimu-phosphate or toother-salt of phosphoric acid.

lt has beenfoundv very desirable. from the commercial standpoint. to circulate a neutral gas, preferably hotl nitrogen, through thereaction zone in close contactWift-h, the charge undergoingy reduction., If no, nitrogen, or like gas, is used. to. carry ofthephosphorus, a thin White glaze forms on the chai-geattenabout of the phosphorushasbeen driven. offy and it then` requires a temperature of.

nearly 30000 F. todrive ofi the phosphorus.

in the charge. lithout a current ofl neutral. gas in` contact with thecharge,I it is prac lll tically impossible to obtain high volatilization rates. For exam le, in a furnace run without nitrogen, a yield of but 28% was obtained and under identical conditions, but vwith nitrogen supplied to the furnace, the yield jumped to I do not limit myself to any particular theory as to the action of the current of neutral gas, but believe its net effect is principally due to the following: it reduces the artial pressure of phosphorus in the atmospliere surrounding the briquets against which the phosphorus vapor must distill; it excludes oxygen and water vapor from the reaction zone, and it prevents secondary reactions between the spent material in the briquet and the phosphorus vapor. One important result of the nitrogen or neutral gas is that it permits the use of a charge of basic character. VIt has been the experience of prior workers in the field of thermal reduction of phosphates that an acid charge is preferable if not necessary. When using the nitrogen current in contact with the charge, the briquets can be made of phos- `phate, carbon and a basic binder without further additions. The normal charge is therefore of the optimum proportions for the volatilization of potash when it isadesired to produce potash along with phosphorus.

The fume passing from the preheating zone consisting principally of P205, 113130 K2(NH4)PO4, together with N2 and CO2 gases and other miscellaneous constituents is then treated to separate the normally solid mineral products from the fixed gases. Preferably this is done in a Cottrell precipitator. The gases, after having been stripped of the normally solid ingredients, are then washed to remove the carbon dioxide and the nitrogen returned to the furnace to assist in carrying off the phosphorus in the charge.

The process according to the present invention, as described above, is preferably carried out in apparatus such as that illustrated in .the drawings. Further details of the process according to the present invention, however, will be apparent from the following description of the apparatus:

Referring to the drawings, 14 is a pulver- .izer which may be used alternately for grinding phosphate rock, coke breeze and calcined dolomite. Pulverizer 14 delivers ground material to a conveyor 16 by which it may be delivered as desired to bins 18, 20 and 22 for 'Sphosphate rock, coke or dolomite respectively.

In making up the furnace charge, rock, coke and dolomite are taken from the bins 18, 20V

and 22 in the proportions above stated and delivered by conduits 24, 24 to a mixer 26 in Vwhich they are thoroughly mixed with each other and with sufficient water so as to make the mass somewhat plastic. The mixture is then delivered to the press 28 and extruded or pressed into plates or briquets. The platesy --ffrom press" 28 pass onto an inclined table 30 are fed either manually or automatically into a chamber 33 having gates or valves 34, 36 (Figs. 2 and 4) at its upper end. The gates 34, 36 are connected by levers 38 and 40 so that one of the gates is always closed. The gases therefore are prevented from escaping from the furnace when briquets are fed into the furnace through the chamber 33.

The furnace illustrated in the drawings is indicated generally by reference character 42. Furnace 42 includes a heat recuperating zone or chamber 48. The portion of furnace 42 which includes the zones 44 and 4G is set at an angle to the horizontal so that its hearth 50 slopes downwardly from the feeding chamber 33 to the vertical recuperator section 48. The furnace 42 has an outer steel shell 51 and it is preferred that the inclination of the hearth 50 be adjustable. As illustrated the hearth 50 may be adjusted about a shaft 43.

Shaft 43 is in the region of the lower end of hearth 50 and a screw-jack 45 is provided ar-` ranged to bear against shell 51 near its upper end to swing the shell 51 about shaft 43. The hearth 50 of furnace 42 extends in an unbroken plane throughout the zones 44 and 46. The upper surface of hearth 50 is in the same plane as the fioor of the inlet chamber 33.

The briquets forming the charge can therey .ing the operation of the furnace by the combustion in chamber 44 of phosphorus fumes and carbon monoxide gas produced in the reduction of the charge in zone 46. The fumes and gas pass from the Zone 46 into zone 44 around the lower edge of the refractory block 54 which forms the lower end of the chamber 44, but which is spaced from the hearth 50 to permit the gases to pass. An opening 56 is formed in muflle 52 to provide an opening into the upper part of chamber 44 above mulle 52 for fumes and gas which have passed upward around the lower end of block 54. Air for combustion of phosphorus and gas in the chamber 44 is admitted thereto through pipe 58. Ammonia water or other substance for reacting with the products of combustion in chamber 44 may also be admitted through pipe 58. The fume and gaseous products of 44 through the pipe 60. Preferably the conditions aremaintained' such in chamber 4.4 that the charge is heatedA under inufiie 52 to a temperature of above 24000 F. before passing into the reduction Zone 46. Considerable reduction may occur before the charge passes from under muifle 52.

After passing the block 54 the charge enters the reduction Zone 46. Within chamber 46 the charge is subjected to the radiant heat of a number of incandescent resistors 62, 62. As illust-rated, resistors 62 preferably are arranged above and parallel to hearth 50, but they may be below the hearth. Resistors 62 extend transversely of the furnace through the side walls thereof,vwhere electrical connections are provided for supplying` current to heat the resistors 62, as indicated at 64, 64 (Fig. 2). Sutiicient current is supplied to the resistors 62 so that preferably the charge in zone 46 is heated to a temperature of approximately 2550o F. As illustrated, the resistors 62 are set above the hearth 50 a suiiicient distance so that the hearth or a thin block or briquet lying thereon will be subjected to substantially uniform heating as it progresses along the hearth. However, refractory blocks 66, 66 preferably are placed one on each side of a given resistor so that gas, such as nitrogen, passing up through the furnace will be forced to pass in close contact with the charge on the hearth.

The charge advances through the furnace in the form of thin plates or briquets 68 some of which are illustrated in position in the furnace at the lower end of Fig. 3. At the lower end of hearth 50, the charge, by this time substantially deprived of its phosphorus content, comes in Contact with a cutter or breaking wheel 7 0 by which the briquets are broken up and fall into avertical shaft 7 2 of the recuperator section 48 o-f the furnace.

In the shaft 7 2, the spent fragments of the charge, composed mostly of lime and magnesia, are cooled by a current of nitrogen entering the section 48 through pipe P4. Within the section 48 the nitrogen passes through flues 76, 76 which surround the shaft '4' 2 and; conduct the nitrogen spirally upward to a port Z8 through which vthe nitrogen discharges against the breaker wheel 70 and'then passes into the reduction zone 46 of the furnace. While passing through the fiues 7 6 the nitrogen recovers heat froml the spent fragments of the charge thereby decreasing the amount of heat lost when the spent fragmentsl are removed from the-furnace and therefore increasing the eiiiciency of the process. The nitrogen, however, is not heated to the full temperature of the charge at the lower end of the Zone 46 and therefore serves to cool' the wheel 7 0 which is in contact with thev spent briquets when at practically their maximum temperature. It is preferred to pass someof thenitrogen. Iinto contact with the bottoinsof briquets on hearth 50; For this purpose, some of the nitrogen is passed from the upper end of iiue 76 through passage 77, appearing in dotted lines in Fig. 3, and into fines 7 9, 79 beneath hearth 50. Individual blocks 80, 80, forming hearth 50, are laid somewhat loosely so that the nitrogen gas escapes from fines 79 upward through the oints in the hearth and against the under surface of the charge on hearth 50'. The path of the nitrogen through the hearth 50 is indicated by arrows 82', 82 on Fig. 3. The rate at which the briquets pass through the furnace depends in part ony the-inclination of the furnace and in part on the speed of the wheel 70. The speed of the' wheel T0v can be readily varied and, according tothe present invention, the furnace 42 is so constructed that its inclination may be varied as desired within certain limits by means of a jack 45 previously mentioned and set in the pier 84 on which the furnace is supported at its upper end. The fragments of spent briquets are discharged from the Zone 48 Aat its bottom through suitable gates 86 andr 88. v

The nitrogen passes up through the furnace in close contact with the charge and assists in carrying off the phosphorus from the charge as it is reduced. t passes out of the furnace with the fume and products of conibustion through the pipe 60. After the fume has been: removed from-the gas stream, the gases are preferably treated for removal of carbon dioxide and other gases which would not be neutral in the furnace and the nitrogen and other neutral gas recirculated through the furnace. Means for carrying out the circulation of lnitrogen as just described includes, in addition to the pipe 60, an appar tus for stripping the fumes from the fixed gases. For this purpose, pipe 60 delivers the fume and gases into a Cottrell precipitator 88. It will be understood that the present invention is not limited to the use of a Cottrell apparatus or other electrical precipitator for recovering the mineral elements from the gases; InY the usualv` operation of the Cottrell precipitator, the gases are commonlyv discharged into the atmosphere after the fume or inist has'been removed therefrom. According to the present invention, however, the Cottrell precipitator is closed at its top and the stripped gases pass out of the precipi-V tator through a pipe 90 by which they are conducted to an absorption tower 92 for the removal of carbon dioxide. As illustrated in the drawings, the apparatus for removing carbon dioxide is one in common use for this purpose in the gas industry and employs sodium carbonate for absorbing the carbon dioxide. The carbon dioxide isrcmoved from the apparatus through pipe 95 in the forml of acid sodium carbonate. The present invention, however,.is not limited to any particular. apparatus or processfor separating: the carbon dioxide from the nitrogen and other neutral gases. From the absorber 92, the nitrogen is returned to the bottom of the furnace by the pipe 74. It has been found in operating a furnace of 600 kw. capacity that a suitlable rate of fiow of nitrogen through the furnace is approximately 21000 cubic feet of nitrogen per hour. In order to circulate the nitrogen and to move the fume and other gases as above described, a fan orgas pump must be provided. As illustrated, a gas pump 91 is connected into pipe 90 to move the gases and fumes through the apparatus. Pump 91 is driven by a direct connected motor 93. 5 Reference has been made to operating the Cottrell apparatus so that the gases are not discharged directly therefrom into the atmosphere. In order to permit this method of operation, the upper ends of the precipitating conduits 94 of the Cottrell apparatus are closed by an insulator 96 supporting the high temperature conductor 98. Difficulty was encountered when it was first attempted to operate the Cottrell apparatus in this manner. It was found that the fume consisting of P205 and other substances would condense on the inner surface and short circuit the apparatus. It has been found possible, however, to heat the insulating plate 96 sufficiently to prevent the collection of fume on its inner surface, thereby preventing difficulty from short circuiting. The conductor 98 is subjected to a considerable electrical tension and dihculty was found in obtaining insulating materials which would withstand the combination of high temperature and high voltage in a highly acid atmosphere. Two materials, however, have been found which will withstand the conditions. One of these is Zircon (zirconium silicate) and the other is fused silica. If Zircon is used, as in the insulator 96, a heating coil 100 may be embedded directly in the body of the insulator at the time it is molded for firing. The Zircon is preferably bonded with a small amount of chromium hydroxide. The method of bonding the zircon, however, forms no part of the present invention and is not claimed herein. If the insulator at the upper end of the section 94 is of fused silica, the heating coil cannot be in corporated into the body of the insulator. In this case, the insulator takes the form of a plate 97 having a heating coil 102 cemented 5 to its outer surface. In actual practice, it has been found that the insulator 96 or 97 should be maintained at or near 12000 F. This temperature is sufficient to prevent condensation of any P205 fog on the insulator. 0 Prior to the discovery of an insulator capable of operating at approximately this temperature, it was impossible to hold more than 45,000 volts between the wire 98 and the conduit 94. After the heated insulator had been 5 installed, it was found possible to maintain as high as 85,000 volts on the precipitator. However, it is not necessary to operateat s0 high a voltage as 85,000. The proper voltage to hold on the wire depends to a considerable.y

degree on the temperature of the gases being treated. The higher the velocity and temperature of the gases the higher theV voltage required on the Cottrell apparatus to obtain good precipitation. In the apparatus in,v

question, it was found diiicult to obtain'good precipitation when the gases reached a temperature of 1200o F. and it is preferred to operate with the gases in the Cottrell apparatus at a temperature near to but below 1000", F. Within this range of temperature, a volt-n age of 55000 'gives good precipitation.

The mixture of P205, I-ISPCi and similar substances precipitated in the Cottrell apparatus 88 may be utilizedv inlvarious 'ways u pipe 103 and delivered to a digester 104..

which is connected by a suitable conveyor indicated diagrammatically in Fig. 1 by reference characters 106 and 108 so as to receive ground phosphate rock from bin 18. The

product formed in digester 104 is then dis-.,

charged into a drier 110. If desired, moreover, the product from drier 110 may be mixed with additional amounts of ground phosphate rock and/or slag in a mixer 112,

the rock and slag being delivered to the inal Y mixer by conveyors 106 and 114 and by conveyor 116.

It will be understood that, while I have disclosed a specific method and apparatus, I

do not limit myself to details of the forego-fing disclosure, it being the intention to claim the novelty embodied in the herein described process and apparatus as broadly as the prior art permits.

It has been found that there is difficulty inr:`

feeding the charge material composed of phosphate and carbon along the hearth, unless the composition of the hearth is of a certain type. It has been found that a hearth formed, of bonded carbon or graphite or of` a graded carborundum aggregate and finely ground magnesia in the proportions by weight of 80% of carborundum to 20% of magnesia is very satisfactory. The later type of material for the hearth, however, forms 'ils 'iso

6 nit-861,236

neiof the presentfinvention endgs not lolainsediherein.

.'Hving l,thus described my invention, I

5 1. Iheprooess ofreducinga phosphate and potash bearing -Ameterial -eomprising mixing ,fthe pllnspimte and fpotash bear-ing tmateriel with .Cambon and a bond contaiI-Iig `mar-gnesia Aand dime, brigueting the mixture and 1 heatiaeg-.thebriquets to aJoove 250001?. lin a swrnentiof. neutra-1 gas x2. Ehe Qprocess `of reducing Vza, phosphate eomprising 2 mixing the phosphate :with `earabxm l:und .a :hond containing magnesia .and 15 biiggietngA thesmixture. andv heating the briquetsgitomboye .25,000 F. in current of muh'aLgas 'lheiprooess-of yreailuGing a .phosphate `elmipgrisigig..Inieiing'sthe phosphate with cai'- 20 Kbon i and ezbond, .ier-ming the `mixture into .hriquetsarrangixig ythe briquets Ain a single 1ligger asma I,prqgressiveljy theatiig -said layer A tofdrive fdihsphorus ,con-taining Y fumes. 4. ELpnocess .of lreducing ,a phosphate "Q25 icon ipriszigmxngfthe trpl-losphate -withearbon and@ :boni forming the mixture linto thin `hat "briquets, .,auranglng the briquets in "a singlelayer and? passing `the san-1e .byggravitythrough@heatingzone, and heating. the "50 -briquetstherein to ,ay Jtemperature suffiient to Heio. osphnnus conteiningfumes.

Intestlmoriy whereof f1 aiix. my signature.

' J O1-IN )MORGAN ses 

